JP2017537464A - Energy storage device and manufacturing method thereof - Google Patents

Abstract

The present invention provides an energy storage device that includes a first electrode, a second electrode, and a solid multilayer structure disposed between the first electrode and the second electrode. The solid multilayer structure may be in contact with the first and second electrodes. The solid multilayer structure may include layers arranged parallel to the electrodes, the layers having the sequence (AB) mA, where A is an insulating layer and B is an insulator. It is a polarization layer containing a colloidal composite having a fine dispersion of conductive nanoparticles in a matrix, and “m” is a number of 1 or more. Layer A can have a breakdown voltage of at least about 0.05 volts / nanometer (nm), and layer B can have a dielectric constant of at least about 100. [Selection] Figure 1

Description

これは容量が面積と共に増加し、距離と共に減少することを示している。したがって、高誘電率の材料で作られたデバイスでは、容量は最大である。 A capacitor is a passive electronic component used to store energy in the form of an electrostatic field and includes a pair of electrodes separated by a dielectric layer. When a potential difference exists between the two electrodes, an electric field is present in the dielectric layer. This electric field stores energy and an ideal capacitor is characterized by a single constant capacitance value that is the ratio of the charge on each electrode and the potential difference between them. In practice, the dielectric layer between the electrodes passes a small amount of leakage current. The electrodes and leads create an equivalent series resistance, and the dielectric layer has a limitation on the electric field strength that results in a breakdown voltage. The simplest capacitor consists of two parallel electrodes separated by a dielectric layer having a dielectric constant ε, each electrode having an area S and arranged at a distance d from each other. The electrode is considered to extend uniformly over the area S, and the surface charge density can be expressed by the formula: ± ρ = ± Q / S. Since the electrode width is much larger than the spacing (distance) d, the electric field near the center of the capacitor is uniform with magnitude E = ρ / ε. The voltage is defined as the line integral of the electric field between the electrodes. An ideal capacitor is characterized by a constant capacitance C defined by equation (1).

This indicates that the capacity increases with area and decreases with distance. Therefore, the capacity is highest in devices made of high dielectric constant materials.

The characteristic electric field, known as the breakdown electric field strength _Ebd , is an electric field at which the dielectric layer in the capacitor becomes conductive. The voltage at which this occurs is called the breakdown voltage of the device and is given by the product of the dielectric strength and the spacing between the electrodes,

The maximum volumetric energy density stored in the capacitor is limited by a value proportional to ~ ε · E ² _bd , where ε is the dielectric constant and E _bd is the breakdown strength. Therefore, in order to increase the stored energy of the capacitor, it is necessary to increase the magnetic permeability ε of the dielectric and the breakdown strength E _bd of the dielectric.

  For high voltage applications, much larger capacitors must be used. There are several factors that dramatically reduce the breakdown voltage. The shape of the conductive electrode is important for these applications. In particular, sharp edges or points can significantly increase the field strength locally, leading to local breakdown. When local breakdown is initiated at an arbitrary location, the breakdown “traces” quickly until it reaches the counter electrode through the dielectric layer and shorts.

  The breakdown of the dielectric layer usually occurs as follows. When the electric field strength is sufficiently high, free electrons from the atoms of the dielectric material conduct current from one electrode to the other. The presence of impurities in the dielectric or imperfections in the crystal structure can lead to avalanche breakdown as observed in semiconductor devices.

  Another important property of the dielectric material is its dielectric constant. Various types of dielectrics are used as capacitors, and there are various types of capacitors such as ceramics, polymer films, paper, and electrolytic capacitors. The most widely used polymer film materials are polypropylene and polyester. Increasing the dielectric constant and volume energy density is an important technical issue.

An in situ polymerization of aniline in an aqueous dispersion of polyacrylic acid (PAA) in the presence of dodecylbenzenesulfonate (DBSA) was used to synthesize a polyaniline ultrahigh dielectric constant complex PANI-DBSA / PAA (Chao- Hsien Hoa et al., “High Dielectric Polyaniline / Poly (Acrylic Acid) Composites Prepared by In Situ Polymerization”, Synthetic Metals 158 (2008), pages 630-637). Water-soluble PAA served as a polymeric stabilizer and protected the PANI particles from macroscopic aggregation. For complexes containing 30% PANI by weight, ca. A very high dielectric constant of 2.0 × 10 ⁵ (at 1 kHz) was obtained. The effect of PANI content on the morphological, dielectric and electrical properties of the composite was investigated. The frequency dependence of dielectric constant, dielectric loss, loss factor and electrical coefficient was analyzed in the frequency range of 0.5 kHz to 10 MHz. SEM micrographs revealed that a composite with a high PANI content (ie 20% by weight) consists of a large number of nanoscale PANI particles evenly distributed within the PAA matrix. The high dielectric constant was attributed to the sum of small capacitors with PANI particles. The disadvantage of this material is the possibility of percolation under the electric field and the formation of at least one continuous conducting path with the probability that such events increase with increasing electric field. When at least one continuous path (track) through adjacent conductive PANI particles is formed between the electrodes of a capacitor, the breakdown voltage of that capacitor is reduced.

  Colloidal polyaniline particles stabilized with a water-soluble polymer, poly (N-vinylpyrrolidone) [poly (1-vinylpyrrolidin-2-one)], were prepared by dispersion polymerization. The average particle size of 241 ± 50 nm was determined by dynamic light scattering (Jaroslav Stejskal and Irina Sapurina, “Polyaniline: Thin Film and Colloidal Dispersion”, Pure and Applied Chemistry, Vol. 77, No. 5). Pp. 815-826 (2005)).

  Single crystals of doped aniline oligomers are produced via a simple solution-based self-assembly method (Yue Wang et al., “Morphological and dimensionality via hierarchical assembly of doped oligoaniline single crystals. Control ", J. Am. Chem. Soc., 2012, 134, pages 9251-9262). Detailed studies on mechanics have shown that crystals of different forms and dimensions can be generated by “bottom-up” hierarchical assemblies, and structures like one-dimensional (1-D) nanofibers can be aggregated into higher order structures. Revealed. A wide variety of crystalline nanostructures, including 1-D nanofibers and nanowires, 2-D nanoribbons and nanosheets, 3-D nanoplates, stacked sheets, nanofloors, porous networks, hollow spheres and torsion coils, control crystals and It can be obtained by non-covalent interaction between the doped oligomers. These nanoscale crystals have improved electrical conductivity compared to their large counterparts and show interesting structural property relationships such as shape-dependent crystallinity. Furthermore, through absorption studies, the morphology and dimensions of these structures can be greatly rationalized and predicted by monitoring molecule-solvent interactions. Using doped tetraaniline as a model system, the results and strategies presented in this paper provide suggestions for a general scheme for organic material shape and size control.

  There are known energy storage devices (capacitors) based on multilayer structures. The energy storage device includes first and second electrodes and a multilayer structure including a barrier layer and a dielectric layer. The first blocking layer is disposed between the first electrode and the dielectric layer, and the second blocking layer is disposed between the second electrode and the dielectric layer. The dielectric constants of the first and second blocking layers are both independently greater than the dielectric constant of the dielectric layer. The disadvantage of this device is that blocking the high dielectric constant layer located in direct contact with the electrodes can lead to the destruction of the energy storage device. High dielectric constant materials based on composite materials and including polarized particles (such as PANI particles) may exhibit a percolation phenomenon. The polycrystalline structure of the formed layer has a plurality of entangled chemical bonds at the boundaries between the crystals. When a high dielectric constant material has a polycrystalline structure, percolation may occur along the boundaries of the crystal grains. Another disadvantage of the known apparatus is the expensive manufacturing procedure, which is the vacuum deposition of all layers.

  Capacitors as energy storage devices have well-known advantages over electrochemical energy storage. Compared to batteries, capacitors can store energy at a very high power density, i.e. charge / recharge rate, have a long storage life with little degradation, hundreds of thousands or millions of times Charging / discharging is possible. However, capacitors often do not store energy in a small volume or weight like batteries and have low energy storage costs, making capacitors impractical for some applications such as electric vehicles. Thus, providing capacitors with high volume and mass energy storage density and low cost can be an advance in energy storage technology.

  The present invention provides an energy storage device (eg, a capacitor) and a method of manufacturing the same. The energy storage device of the present invention can solve the problem of further increase in the volume and mass density of stored energy associated with some energy storage devices while simultaneously reducing the cost of materials and manufacturing processes.

In one form, the capacitor includes a first electrode, a second electrode, and a solid multilayer structure disposed between the first and second electrodes. The electrodes are planar and arranged parallel to each other, and the solid multilayer structure includes layers arranged parallel to the electrodes and has the following sequence: (AB) _m -A. Here, A is an insulating layer, B is a polarization layer including fine dispersion of conductive nanoparticles in an insulator matrix, and several m ≧ 1. In some cases, m is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 100, 200, 300, 400, 500, 600 or more. possible. In some examples, m is 1-1000, 1-100, or 1-50. The electrodes may be substantially parallel to each other or substantially parallel. The electrodes can be offset from the parallel arrangement.

  In another form, a method of manufacturing a capacitor includes: (a) preparing a conductive substrate that functions as one of the electrodes; (b) forming a solid multilayer structure; and (c) forming a second electrode on the multilayer structure. Formation of the multi-layer structure, including formation, includes the step of alternating application of the insulating and polarization layers or the step of co-extrusion of the layers.

  In another form, a method of manufacturing a capacitor includes coating an insulating layer on both electrodes, and laminating a second electrode in a multilayer structure and coating one of the electrodes with the multilayer structure.

  Further aspects and advantages of the present invention will become readily apparent to those skilled in the art from the following detailed description, wherein only exemplary embodiments of the invention are shown and described. As will be realized, the invention is capable of other and different embodiments, and its several details are capable of modifications in various respects, without departing from the invention. Accordingly, the drawings and descriptions are to be regarded as illustrative in nature and not as restrictive.

INCORPORATION BY REFERENCE All publications, patents and patent applications mentioned in this specification should be considered in the same manner as individual publications, patents or patent applications are specifically and individually indicated to be incorporated by reference. Which is incorporated herein by reference.

  The novel features of the invention are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings of which:

1 schematically illustrates an energy storage device according to some embodiments of the invention. Fig. 3 schematically illustrates another energy storage device according to some embodiments of the invention.

  While various embodiments of the invention have been shown and described herein, it will be apparent to those skilled in the art that such embodiments are provided by way of example only. Many variations, modifications and substitutions may occur to those skilled in the art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described herein can be used.

The present invention provides an energy storage device such as a capacitor. In one embodiment of the invention, the insulating layer is crystalline. The insulating layer can be made from any suitable crystalline material, including single crystal materials, batch crystal materials, or amorphous materials. Depending on the application, the dielectric constant of the insulating dielectric material can be in a wide range. The insulating layer has a band gap greater than 4 eV, and about 0.001 volts (V) / nanometer (nm), 0.01 V / nm, 0.05 V / nm, 0.1 V / nm 0.2 V / nm,. Includes materials characterized by breakdown field strengths greater than 3 V / nm, 0.4 V / nm, 0.5 V / nm, 1 V / nm, or 10 V / nm. The material of the polarization layer has a dielectric constant ε _pol that can be in a wide range. In some cases, ε _pol is at least about 100, 200, 300, 400, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10,000 or 100,000.

式中、Ｃｏｒは共役π系を有する多環式有機化合物であり、Ｍは修飾官能基であり、ｎは修飾官能基の数で、１以上となる。本発明の別の実施形態では、多環式有機化合物は、オリゴフェニル、イミダゾール、ピラゾール、アセナフテン、トリアジン、インダントロン、およびそれらの混合物からなるリストから選択される。表１に示す構造１〜４３から選択される一般構造式を有する。

In the present invention, the solid insulating dielectric layer can have a different structure in the range between the amorphous layer and the crystalline solid layer, depending on the materials used and the manufacturing procedure. In one embodiment of the disclosed capacitor, the insulating layer comprises a material selected from oxides, nitrides, oxynitrides and fluorides. In another embodiment of the disclosed capacitor, the insulating layer comprises a material selected from SiO ₂ , HFO ₂ , Al ₂ O ₃ or Si ₃ N ₄ . In one embodiment of the disclosed capacitor, the insulating layer has the general structural formula I:

In the formula, Cor is a polycyclic organic compound having a conjugated π system, M is a modified functional group, and n is the number of modified functional groups, which is 1 or more. In another embodiment of the invention, the polycyclic organic compound is selected from the list consisting of oligophenyl, imidazole, pyrazole, acenaphthene, triazine, indanthrone, and mixtures thereof. It has a general structural formula selected from structures 1 to 43 shown in Table 1.

In another embodiment of the invention, the modified functional group is selected from a list comprising alkyl, aryl, substituted alkyl, substituted aryl, and any combination thereof. The modified functional group provides the solubility of the organic compound at the manufacturing stage and further insulating properties of the solid insulating layer of the capacitor. In yet another embodiment of the invention, the insulating layer is a polymer selected from the list comprising fluorinated alkyl, polyethylene, kevlar, poly (vinylidene fluoride-hexafluoropropylene), polypropylene, fluorinated polypropylene, polydimethylsiloxane. Contains materials. In yet another embodiment of the invention, the insulating layer comprises a polymeric material formed based on a water soluble polymer selected from structures 44-49 shown in Table 2.

修飾官能基Ｒ_１およびＲ_２は、アルキル、アリール、置換アルキル、置換アリール、およびそれらの任意の組み合わせを含むリストから独立して選択される。 In another embodiment of the invention, the insulating layer comprises a polymeric material formed based on a polymer soluble in an organic solvent selected from structures 50-55 shown in Table 3.

The modified functional groups R ₁ and R ₂ are independently selected from the list comprising alkyl, aryl, substituted alkyl, substituted aryl, and any combination thereof.

ただし、Ｘ＝２、３、４、５、６、７、８、９、１０、１１、１２である。本発明のコンデンサの別の実施形態では、分極層は、低分子化合物の導電性ナノ粒子を含み、この導電性ナノ粒子は、分子量の導電性ポリマーである。本発明の別の実施形態において、低分子導電性ポリマーは、表４に与えられるような構造５７〜６３から選択される部分を含む。開示されるコンデンサの別の実施形態において、導電性オリゴマーは、置換基をさらに含み、一般構造式ＩＩ：

ここで、Ｒ_ｑは置換基の集合であり、ｑは集合Ｒ_ｑにおける置換基Ｒの数であり、ｑは０、１、２、３、４、５、６、７、８、９または１０に等しいことができる。コンデンサの別の実施形態では、置換基Ｒは、アルキル、アリール、置換アルキル、置換アリール、およびそれらの任意の組み合わせを含むリストから独立して選択される。コンデンサのさらに別の実施形態では、絶縁体マトリックスの材料は、ポリ（アクリル酸）（ＰＡＡ）、ポリ（Ｎ−ビニルピロリドン）（ＰＶＰ）、ポリ（フッ化ビニリデン−ヘキサフルオロプロピレン）［Ｐ（ＶＤＦ−ＨＦＰ）］、エチレンプロピレンゴム（ＥＰＲ）およびエチレンプロピレンジエンモノマー（ＥＰＤＭ）を含むエチレンプロピレンポリマー、およびジメチルジクロロシロキサン、ジメチルシランジオールおよびポリジメチルシロキサンなどのシリコーンゴム（ＰＤＭＳＯ）を含む。これらの化合物は安定剤としても機能し、導電性ナノ粒子を巨視的凝集から保護する。開示されたエネルギー蓄積デバイスの電極は、Ｐｔ、Ｃｕ、Ａｌ、Ａｇ、Ａｕ、Ｔｉ、Ｗ、Ｚｎ、Ｎｉまたは他の低融点合金を含むがこれらに限定されない任意の適切な材料から作製され得る。本発明の一形態では、絶縁層の厚さ（ｄ_ｉｎｓ）と、分極層の厚さ（ｄ_ｐｏｌ）と、絶縁層の絶縁破壊電界強度Ｅ_ｉｎｓと、偏波層の絶縁破壊電界強度Ｅ_ｐｏｌとは、ｄ_ｉｎｓ＜ｄ_ｐｏｌ、およびＥ_ｉｎｓ＞Ｅ_ｐｏｌという関係がある。 In one embodiment of the invention, the polarization layer is crystalline. In one embodiment of the present invention, the polarization layer comprises nanoparticles of conductive oligomers. In another embodiment of the invention, the longitudinal axis of the conductive oligomer is oriented primarily perpendicular to the electrode surface. In one embodiment of the invention, the conductive oligomer is selected from a list comprising the following structural formula corresponding to one of structural formulas 57-63 shown in Table 4.

However, X = 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12. In another embodiment of the capacitor of the present invention, the polarization layer comprises a low molecular weight compound conductive nanoparticle, which is a molecular weight conductive polymer. In another embodiment of the invention, the small molecule conductive polymer comprises a moiety selected from structures 57-63 as given in Table 4. In another embodiment of the disclosed capacitor, the conductive oligomer further comprises a substituent and has the general structure II:

Where R _q is a set of substituents, q is the number of substituents R in the set R _q , and q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 Can be equal to In another embodiment of the capacitor, substituent R is independently selected from a list comprising alkyl, aryl, substituted alkyl, substituted aryl, and any combination thereof. In yet another embodiment of the capacitor, the insulator matrix material is poly (acrylic acid) (PAA), poly (N-vinylpyrrolidone) (PVP), poly (vinylidene fluoride-hexafluoropropylene) [P (VDF -HFP)], ethylene propylene polymers including ethylene propylene rubber (EPR) and ethylene propylene diene monomer (EPDM), and silicone rubbers (PDMSO) such as dimethyldichlorosiloxane, dimethylsilanediol and polydimethylsiloxane. These compounds also function as stabilizers and protect the conductive nanoparticles from macroscopic aggregation. The electrodes of the disclosed energy storage devices can be made from any suitable material including, but not limited to, Pt, Cu, Al, Ag, Au, Ti, W, Zn, Ni or other low melting point alloys. In one embodiment of the present invention, the thickness of the insulating layer (d _ins ), the thickness of the polarization layer (d _pol ), the dielectric breakdown field strength E _ins of the insulation layer, and the dielectric breakdown field strength E _{pol of the} polarization layer. And d _ins <d _pol and E _ins > E _pol .

In another embodiment of the present invention, the electrode is made of copper, the number m is 1, the dielectric material of the insulating layer A is polyethylene, and the material of the polarizing layer B is a finely dispersed PANI-DBSA / PAA dodecylbenzenesulfonate ( Synthesized using in situ polymerization of aniline in an aqueous dispersion of polyacrylic acid (PAA) in the presence of DBSA), the ratio of PANI to PAA in the composite was 20% by weight of insulating layer thickness The thickness is d _ins = 25 nm, and the thickness of the polarization layer d _pol = 10 mm. In yet another embodiment of the invention, the electrode is made of copper, the number m is equal to 1, the dielectric material of the insulating layer A is polyethylene, and the material of the polarizing layer B is poly (N-vinylpyrrolidone) (PVP). The thickness of the insulating layer is d _ins = 25 nm, and the thickness of the polarization layer d _cond = 50 μm. In another embodiment of the present invention, the polarizing layer comprises dodecylbenzene sulfonate (DBSA), polyoxyethylene glycol alkyl ether, polyoxypropylene glycol alkyl ether, polyoxyethylene glycol octyl phenol ether, polyoxyethylene glycol sorbitan alkyl ester, sorbitan. Alkyl ester, dodecyldimethylamine oxide.

  The present invention also provides a method for manufacturing the above capacitor. In one embodiment of the disclosed method, step (b) of forming the multilayer structure comprises alternating steps of applying a solution of insulating material and applying a solution of polarizing material, and after both application steps, drying Forming a solid insulating layer and a polarizing layer, and the alternating steps are repeated until the formation of the multilayer structure is completed, so that the first layer and the last layer are in direct contact with the electrode. Is formed. In another embodiment of the disclosed method, the step (b) of forming the multilayer structure comprises alternating steps of applying a melt of insulating material and applying a melt of polarizing material, after both application steps. Has a step of cooling to form a solid insulating layer and a polarizing layer, and the alternating steps described above are repeated until the formation of the multilayer structure is complete, with the first and last layers in direct contact with the electrode Thus, an insulating layer is formed. In yet another embodiment of the disclosed method, the step (b) of forming a solid multilayer structure comprises co-extruding onto the substrate a set of layers comprising successive alternating polarization materials and insulating dielectric materials. Including, and thereafter, drying to form a solid multilayer structure. In yet another embodiment of the disclosed method, forming the solid multilayer structure includes coextruding a set of layers that continuously comprise alternating melts of polarizing and insulating dielectric materials. Thereafter, it has a step of cooling to form a solid multilayer structure. Further, the present invention includes (d) a step of coating an insulating layer on both electrodes, and (e) a step of coating a multilayer structure on one electrode and coating a second electrode on the multilayer structure. A method for manufacturing the above capacitor is provided.

Example 1
FIG. 2 shows an embodiment of the disclosed energy storage device comprising a solid multilayer structure comprising electrodes 1 and 2 and two insulating layers of insulating dielectric (3 and 4) separated by a polarizing layer (5). . In this embodiment of the invention, polyaniline and PANI-DBSA / PAA synthesized using in situ polymerization of aniline in an aqueous dispersion of polyacrylic acid (PAA) in the presence of dodecylbenzenesulfonate (DBSA) These composites are used as the material for the polarization layer, and polyethylene is used as the insulating dielectric material. The thickness d _ins of the insulating layer is 2.5 nm. The electrodes 10 and 11 are made of copper. The dielectric constant of polyethylene is equal to 2.2 (ie, ε _ins = 2.2). The complex of polyaniline and PANI-DBSA / PAA has a dielectric constant ε _pol of 100,000, and the thickness of the conductive layer having molecular conductivity is d _pol = 1.0 mm.

Example 2
FIG. 3 shows an embodiment of the disclosed energy storage device comprising electrodes 6 and 7 and a solid multilayer structure comprising alternating insulating and polarizing layers, wherein the layers of insulating dielectric material (11, 12, 13, 14) Are separated by polarization layers (8, 9, 10). In this embodiment of the present invention, a PANI-DBSA / PAA composite material is used as the material of the polarization layer, and polyethylene is used as the insulating dielectric material. Insulating layer thickness = 2.5-1000 nm. Electrodes 6 and 7 are made of copper. The dielectric constant of polyethylene is 2.2 (ie, ε _ins = 2.2), and the dielectric breakdown voltage V _bd = 1 millimeter is 40 kilovolts thick. In one embodiment, the material of the polarization layer is a polyaniline (PANI) / poly (acrylic acid) (PAA) composite material having a dielectric constant ε _pol equal to 100,000. In this example, the polarization layer thickness d _pol = 1.0 to 5.0 mm.

  Although the present invention has been described in detail with reference to certain preferred embodiments, various modifications and improvements can be made by those skilled in the art without departing from the spirit and scope of the claims. .

  While preferred embodiments of the present invention have been shown and described herein, it will be apparent to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions can be made by those skilled in the art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described herein can be employed in the practice of the invention. The following claims define the scope of the invention and are intended to cover the methods and structures within these claims and their equivalents.

Claims (31)

A first electrode;
A second electrode;
A solid multilayer structure disposed between the first electrode and the second electrode;
Have
The solid multilayer structure is in contact with the first and second electrodes and includes a layer disposed parallel to the electrode, the solid multilayer structure comprising a sequence of the layers (AB) _m -A Where A is an insulating layer, B is a polarization layer containing a colloidal composite having a fine dispersion of conductive nanoparticles in an insulator matrix, and m is a number of 1 or more. ,
A has a breakdown voltage of at least about 0.05 volts (V) per nanometer (nm);
A capacitor wherein B has a dielectric constant of at least about 100.   The capacitor according to claim 1, wherein at least one of the insulating layers is crystalline.   The capacitor of claim 1, wherein A has a breakdown voltage of at least about 0.5 V / nm.   The capacitor of claim 1, wherein at least one of the insulating layers comprises a material selected from oxides, nitrides, oxynitrides, and fluorides. The capacitor of claim 4, wherein at least one of the insulating layers comprises a material selected from SiO ₂ , HFO ₂ , Al ₂ O ₃ , and Si ₃ N ₄ . At least one of the insulating layers comprises a modified organic compound of general structural formula I;

The capacitor according to claim 1, wherein Cor is a polycyclic organic compound, each M is independently a modified functional group, n is the number of modified functional groups, and is 0 or more. The capacitor of claim 6, wherein the polycyclic organic compound is selected from oligophenyl, imidazole, pyrazole, acenaphthene, triazine, indanthrone, and structures 1-43.

  The capacitor of claim 6 or 7, wherein the modified functional group is selected from alkyl, aryl, substituted alkyl, and substituted aryl.   The at least one of the insulating layers comprises a compound selected from fluorinated alkyl, polyethylene, Kevlar, poly (vinylidene fluoride-hexafluoropropylene), polypropylene, fluorinated polypropylene, and polydimethylsiloxane. Capacitor. The capacitor of claim 1, wherein at least one of the insulating layers comprises a material having a structure selected from structures 44-49.

At least one of the insulating layers comprises a material having a structure selected from structures 50-55;

The capacitor of claim 1, wherein each R ₁ and R ₂ is independently selected from alkyl, aryl, substituted alkyl, and substituted aryl.   The capacitor of claim 1, wherein at least one of the polarization layers is crystalline.   The capacitor according to claim 1, wherein the conductive nanoparticles include a conductive oligomer.   The capacitor of claim 13, wherein the longitudinal axis of the conductive oligomer is oriented perpendicular to the electrode surface. The conductive oligomer is any one of structural formulas 57 to 63,

The capacitor according to claim 13, wherein X = 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.   The capacitor of claim 1, wherein the conductive nanoparticles comprise a low molecular weight conductive polymer. The low molecular weight conductive polymer comprises a monomer corresponding to any one of structural formulas 57 to 63;

The capacitor according to claim 16, wherein X = 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. The conductive oligomer is represented by the following formula:

The capacitor according to claim 13, wherein R _q is a substituent, and q is a number of 0 or more.   The capacitor of claim 18, wherein each R is independently alkyl, aryl, substituted alkyl, or substituted aryl.   The insulator matrix material is poly (acrylic acid) (PAA), poly (N-vinylpyrrolidone) (PVP), poly (vinylidene fluoride-hexafluoropropylene) [P (VDF-HFP)], ethylene propylene rubber 2. The ethylene propylene polymer comprising (EPR) and ethylene propylene diene monomer (EPDM), and silicone rubber (PDMSO) such as dimethyldichlorosiloxane, dimethylsilanediol and polydimethylsiloxane. Capacitor.   The capacitor according to claim 1, wherein at least one of the electrodes includes Pt, Cu, Al, Ag, Au, Ti, W, Zn, Ni, or a low melting point alloy. The relationship among the thickness of the insulating layer (d _ins ), the thickness of the polarizing layer (d _pol ), the breakdown electric field strength E _ins of the insulating layer, and the dielectric breakdown electric field strength of the polarizing layer E _pol is _expressed as d _ins <d _pol. And the capacitor of claim 1, wherein E _ins > E _pol . The electrode contains copper, m is 1 or more, the dielectric material of the insulating layer A is polyethylene, the material of the polarization layer B is finely dispersed PANI-DBSA / PAA, and the ratio of PANI to PAA in the composite layer Is about 20% by weight or more, the insulating layer has a thickness (d _ins ) of at least about 2.5 nm, and the polarizing layer has a thickness (d _pol ) of at least about 1.0 mm. The capacitor according to claim 1. Colloid in which the electrode contains copper, m is 1 or more, the dielectric material of the insulating layer A is polyethylene, and the material of the polarizing layer B is stabilized by poly (N-vinylpyrrolidone) (PVP) It is a PANI dispersion, and the thickness (d _ins ) of the insulating layer is 2.5 to 1000 nm, and the thickness (d _cond ) of the polarization layer is 10 to 50 μm.   The polarizing layer comprises dodecyl benzene sulfonate (DBSA), polyoxyethylene glycol alkyl ether, polyoxypropylene glycol alkyl ether, polyoxyethylene glycol octyl phenol ether, polyoxyethylene glycol sorbitan alkyl ester, sorbitan alkyl ester, and dodecyldimethylamine oxidation. The capacitor according to claim 1, further comprising a surfactant selected from an object. A method for manufacturing a capacitor, comprising:
a) providing a conductive substrate that functions as a first electrode;
b) forming a solid multilayer structure adjacent to the first electrode;
c) forming a second electrode adjacent to the multilayer structure;
However, the step of forming the multilayer structure includes alternating operations of applying insulating layers and polarizing layers or co-extrusion operations of insulating layers and polarizing layers, wherein each insulating layer is at least about 0.05 volts per nanometer (nm) And the individual polarization layers have a dielectric constant of at least about 100.   The step of forming the solid multilayer structure includes an alternating operation of applying a solution of an insulating material and applying a solution of a polarizing material, and drying both of the applying operations to form a solid insulating layer and a polarizing layer. 27. The method of claim 26, comprising alternating steps, wherein the alternating operation is repeated until formation of the multilayer structure is complete, and the insulating layer is formed such that the first and last layers are in direct contact with the electrode. The method described.   The step of forming the solid multilayer structure includes alternating operations of applying a melt of insulating material and applying a melt of polarizing material, and after both applying operations, the solid insulating layer and the polarizing layer are cooled. The alternating operation is repeated until the formation of the multilayer structure is completed, and the insulating layer is formed such that the first layer and the last layer are in direct contact with the electrode. Item 27. The method according to Item 26.   Forming the solid multilayer structure comprises co-extruding onto the substrate at least one set of the layers sequentially comprising alternating polarization materials and insulating dielectric materials and then drying to form the solid multilayer structure 27. The method of claim 26, comprising:   The step of forming the solid multilayer structure includes the step of coextruding the set of layers comprising an alternating melt of polarization material and insulating dielectric material, followed by cooling to form the solid multilayer structure. 27. The method of claim 26, wherein: A method for manufacturing a capacitor, comprising:
a) coating an insulating layer on the first and second electrodes;
b) coating a multilayer structure on one insulating layer of the first and second electrodes, laminating the other of the first and second electrodes in the multilayer structure,
A method of manufacturing a capacitor, wherein each insulating layer has a breakdown voltage of at least about 0.05 volts / nanometer (nm) and the multilayer structure includes a polarizing layer having a dielectric constant of at least about 100.

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